4(1)-halo-1(4)-acyloxyvaleric acid and derivatives and preparation thereof



Patented'Nov. 9, 1943 pany, Rochester, Jersey No Drawing.

Application September Serial No.355','8,75,

N. Y., a corporationpflNew teams. 11. 260-484) This inventionirelates to valeric acid compounds andtoI ajprocess torfthepreparation thereof. More particularly, it relates'tooompoundscharacterized by one of the renewing formulas:

wherein R' represents 1 hydrogen, an alkyl group such as methyl, ethyl, propyl, butyl, cetyl, methoxymethyl, methoxyethyl, ethoxybutyl or an alkali-forming metal such as sodium, potassium, calcium and the like, X representsa halogen atom and Z'represents-hydrogeri oran acyl group such as acetyl, propionyl, butyryl, valeryl, stearyl, benzoyl, naphthoyl and other similar kind of groups. Further, the nuclei of the benzoyl and naphthoyl groups can be substituted by one or more monovalent substituentsfromthe group including chlorine, bromine, methyl, ethyl, butyl, methcxy, ethoxy, butoxy, sulfondimethylamide or the like groups. 7 Y

We have found that our new 4(1)halo-1(4)- acyloxyvaleric acids and derivatives above described are .valuable plasticisers and softening agents for organic derivatives of cellulose such as cellulose nitrate, cellulose formate, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose phthalate, cellulose acetate-propionate, cellulose acetate-butyrate, methyl cellulose, ethyl cellulose, benzyl cellulose and the like, vinyl resins including vinyl alkyl ketone resins, and vinyl acetal resins, phenol aldehyde resins, indene resins, and other similar kind of synthetic resinous materials. In addition to their plasticizing properties, our new compounds are also valuable intermediates for the preparation of amino acids. Further, by reacting our compounds with aniline or a-naphthylamine and their derivatives, compounds can be obtained which are valuable as couplers in the preparation of dyes such as azo, indophenol and anthraquinone, as

well as coupling components in various photothe presence of a metallic halide catalyst. The products) obtained by distillation of'the reaction mixtureconsists of a greater portion of the 4;- haId-L-acyloxyvaleric acid compound andla' lesser portion of the l-halo-4-acyloxyvaleric 'acid' com"- pound'. As acyl halides there'can be' employed the acid chlorides, acid bromides, acid fluorides or-acid iodides of aliphatic and. aromatic acids suchas acetic, propionic, butyric, valeric, stearic, benzoic and naphthoic acids. The catalyst can be the chloride, bromide, fluoride oriodide of Zinc, or, the corresponding halide-of titanium or boron, as Well as a halide of"zirconium, aluminum, iron, beryllium, nickel, tin or molybdenum. When the 4(1)-halo-1'(4)-acyloxyvaleric acid compounds above described are hydrolyzed with an excess of aqueous caustic sodasolution, there is obtained lA-dihydroxyvaleric acid. If the hydrolyzing agent is a mineral acid instead of caustic soda, the compound obtained-is a 4(1)-halo- 1.(4)-hydroxyivaleric acid.

The invention is. illustrated further by the following examples describingthe, preparation of numberof our new compounds.

Example 1 A mixture of 1 mole of ethyltetrahydrofuroate,- 1.1 moles of acetyl chloride, and 0.5 gram of zinc chloride was heated under reflux on a. steam bath for about one hour, and then distilled under reduced pressure. There was obtained a good yield of 4-chloro-l-acetoxy-ethylvalerate, and a smaller yield of the isomeric l-chloro--acetoxyethylvalerate.

Example 2 A mixture of 1 mole of methyltetrahydrofuroate, 1.1 moles of acetyl bromide, and 0.5 gram of zinc bromide was heated on a steam bath for a period of about 1.5 hours, and then distilled. A good yield of 4-bromo-l-acetoxy-methylvalerate was obtained, the main portion having a boiling range of 135 C. at 10 mm. pressure. By subjecting the above compound to an acid hydrolysis with hydrochloric acid, 4-bromo-1-hydroxyvaleric acid was obtained as a product.

Example 3 1 mole of propyltetrahydrofuroate was heated on a steam bath with 1.1 moles of propionyl fluoride and a small quantity of zinc chloride as a catalyst. When the reaction was complete, the mixture was distilled and the product l-fluorol-propionoxypropylvalerate obtained in good yield, the main portion having a boiling range of -145 C. at 13 mm. pressure.

Example 4 1 mole of tetrahydrofuroic acid was heated with 0.5 gram of zinc chloride on a steam bath and then 1 mole of acetyl chloride added slowly with stirring. A good yield of 4-chloro-1-acetoxyvaleric acid was obtained'by distilling the reaction mixture.

Example 5 was boiled with 4 mole equivalents of aqueous sodium hydroxide. When the halogen had g s all been removed, the reaction mixture uwas cooled, and made slightly acid toCongo red with hydrochloric acid. The 1,4-dihydroxyvaleric acid formed by this reaction was recovered by ex- 1 mole of 4-chloro-1-benzoyloxy-phenylvalerate traction with ethyl ether. The purified product was a colorless, viscous liquid which formed a lactone on heating.

Emmple 6 A mixture of 1 mole of 3-methyltetrahydrofuroic acid ethyl ester, 1 mole of benzoyl iodide and 0.5 gram of zinc chloride was heated on a steam bath. The product 4-iodo-l-benzoyloxy ethylvalerate was purified by crystallization.

Example 7 1 mole of ethyltetrahydrofuroate. was reacted with 1.1 moles of ethylchlorocarbonate follow-. ing the procedure of Example 1. The resulting product 4-ch1oroe1-ethoxycarboxy ethylvalerate was purified by crystallization.

We claim:

1. A valeric acid compound having the general formula:

X 0111- om- 011,- c11 0 0 o R wherein R represents a member selected Irom the group consisting of hydrogen, an alkyl group,

and an alkali-forming metal, X represents a halo- 1 gen, and Z represents an acyl group.

2. A valeric acid compound having the general formula:

X-CHz-CHr-CHz-CH-OOOR wherein R represents a member selected from the group consisting of hydrogen, an alkyl group, and an alkali-forming metal, X represents a halogen. and Z represents an acetyl group.

3. A valeric acid compound having the general formulai Q x-cm-cm-om-on-ooon 'gwherema represents amember selected from the group consisting of hydrogen, an alkyl group, and an alkali-forming metal, X represents a halogen, and Z represents a benzoyl group.

4. A process for preparing a 4-halo-1-acyloxyvaleric acid comprising reacting an acyl halide with a tetrahydrofuroic acid in the presence of a metallic halide catalyst.

5. A process for" preparing 4-halo-1-acy1oxyvaleric ester comprising reacting an acyl halide with a tetrahydrofuroic acid alkyl ester in tK' presence of a metallic halide catalyst.

6., A process for. preparing a 4'-halo-1-hy droxyvaleric acid comprising, reacting anacyl halide .wherein X represents halogen.

9. A process-for preparing a 4-lialo-l-acyloxyvaleric compound comprising reacting'an acyl halide with a compound selected from the group consisting of tetrahydrofuroic acid and tetrahydrofuroic acid alkyl esters, in the presence of a metallic halide catalyst.

JOSEPH B. DICKEY. ROBERT A. 'CORBITT. 

